Manufacture of aliphatic ijnsatu-



UNlTED'f STATES ;-PATENT OFFICE l v is I i I MANUFACTUR ALIPH'ATIOUNSAT .nA r oNrrRo COMPQUNDS' p ,1 HerbertSchwarz, Leverlrusen-Wiesdorf,and EJoh'an'n'es Nelles, Leverkusen- SchlebuschyGer- J .:,m any, assignors, by *mesne assignments 'to i General Aniline & Film Corporation, New York,

N; Y., a corporation of Delaware 2 *No Drawing. Application August 2, 1939,-; Seria No.287,932 GermanyfAu'g ustjl 1932i new-process 5 V l s-The present invention relates .tovv V 'Ior 'preparing "aliphatic .unsaturat pounds.

d-niimcomu ik r ib ll f i wheat f Y atoms, it being to be understood thatthe presence =It'is known-thatunsaturated mitrocompounds. of aromaticradicals in the acyl group and/or in ..canL-b'eaobtainedibyccausingaromatic-aldehydes 5 the side chains,is."not' -exuludedeirom he'y scope, .wsuch as benzaldehyde* to""reactiupon nitro- ,o f our irilr'entipmillgpendin ori-lth methalne. Contrary thereto, the-interactionbf V thejstartingmaterialsfthe rea.

" aliphatic or. ar'aliphatic; aldehydes. or ketonesand termed byus'i mply. allowingthe Qacyla 7 al phatic n t ocompounds re u s in t formal: a zh d o yn t compopnd and the alkaline 1rje me, A e tion;of p hydroxynitrocompounds, it being conilsub'stajnce-t standat ordiri'a temperature-pi hy I nected with diflicult'ies to vefiect'the splitting, off heatin'lgsthe mixturevthereo Ihe=, use gt diluents of water from such compounds and to convert can be dispensed with. The 'unsaturated'nitro the same into the desired unsaturated products. compounds can be isolated from the reaction 1 Weare aware of the factthat in accordance with mixture by distillation. In case of working 'in I a process described in literature lunsaturated the heat, the unsaturated nitro compounds'can nitr'oc'oinpounds have been obtained by causing be continuously removed by distillation. V V alkali metal, carbonates in excess to react upon Thefollowing examples illustrate our presentl acylated I aliphatic fi hydroxynitrocompounds. invention without; however, restricting'it thereto, r I Such conditions have provedto' be unsuitable for theparts'being by weight. I Y 1 thefpr'eparation of lower unsaturated aliphatic V V r 7 Example 1 nltrocompounds in a techmcal scale as owing to 1 c y 7 v the excess alkali metal carbonate undesirable by- 72 P of f P wa d j reactions can not be avoided. Also in case higher p 'O anhydrous sodium acetate'are trea ed unsaturated aliphatic nitrocompounds are inhalf n our at 100C. The mixture is distilled r tended, for instance, those containing at least 8 under reduced P u e until the V brownish carbon atoms, the prior method failedto'yield a Colored sidue begins to crystall There, satisfactory result as the reaction proceeds ,too Obtained 61 parts of a mixture consisting of slowly for being suitable for technical purposes; m c d and mp py e \'The solution is In each case the prior method requires 'the W ed with a Saturated solution of common salt presence of a iluent u as t J Y until becoming free from acetic acid and there- It is an object of ourr presentiinvention to do I 1 0 dried by m n of a c um chloride. There s l away with these disadvantages andto develop a is obtained a, yield of 33 parts of pure 'nitroprocess which allowsone to prepare aliphatic'unpropylenei-the boiling PO t being C- 81715 saturated nitrocompounds ina jgood'yield andin Pressure ea theoretical y eld of 78%)- a manner which fits the practicaldemands of a Example 2 r 7 technical preparation. Other, objects of our in.-, 7 7 1 D V vention will be apparent from, the following de- Parts offl'mfimpmpylpmpmnate and 1 1 sripnon and claims. i 0.2 part of potassium'carbonate are treated as Weihave found that all disadvantages inherent descnbed Example. Obtained24 i v h prior known method n be overcomervby 0 partsv of -mtropropylene (l.-e. a theoretical yield A employing the alkaline reacting substances, which of a V i a i are reacted upon the aliphatic O.acylated gp-i, j I Example \3 V I h d o ou ds. in a amount which 587 parts of 1-nitropentano1-2-acetateVand.0;5

- below the stoichiometric amount, preferably in 45 part of sodium hydmxyae are stirred at C. an amount of betwenrabout and out 10% When the whole sodium hydroxide has dissolved I (calculated up the o-acylated fi-h yn t (after about 1 hour), the acid is distilled 01! at D n The term alkaline reading Sllbabout 16 mm. pressure. 'The residue is washed stances comprises alkali metal "h d with water; dried byimeans of calcium chloride earth alkali metal-hydroxides as well as salts of d thereupon distilled I at 16 mm. pressure. Such metals With weakracids- Examples for the There are obtained 330 parts of nitroamylene,

r I latter are'sodium c rbo Sodium biCarbOHate, the boiling point being 73 C. at16 mm; pressure sodium acetate and the like. Furthermore,there I a theoretical yield Qf,V94%) I p 7 Example 4 I r 672 partsioif 1-nitropentano1-2 are 'acetylated" can be employed organic amines, such as piperi- I dine. The term"aliphatic O.acylated c-h'ydroxynitrocompounds is intended to define such comwith 515 parts of acetic acid anhydride with addition of 0.2 part of concentrated sulfuric acid. The crude mixture is mixed with parts of anhydrous sodium acetate and the whole acetic acid is distilled 011.011 the water bath. The residue is further treated as described in Example 3. There are obtained 483 parts of nitroamylene (i. e. a theoretical yield of 83%).

Example 5 253 parts of fi-nitrooctylacetate and 0.2 part of anhydrous sodium acetate are 'treated as described in Example 3. There are obtained 153 parts of nitrooctylene, the boiling point being 118420 0. at mm. pressure (1. e. a theoretical yield of 83%);

Example 6 parts of O-acetyI 4 1 nitro 4 methoxy pentanol-2 and 0.2 part of anhydrous sodium acetate are treated-as described in Example 3. There are obtained 23 parts or pure-'i-methoxynitroamylene of the boiling point 110 C. at 15 mm. pressure (1. e. a theoretical yield of Example 7 V parts of 2 methyl 3 nitropentanol 4 distilled at 14 mm. pressure. It is obtained in a yield of 29 parts and shows the boiling point 67-70 C. at 14 mm. pressure. 28 parts of unchanged acetate can be recovered Irom the residue of the distillation. Accordingly there is obtained a theoretical yield of 60%.

Example 8 100 parts of 3 methyl 2 nitro-butanol 1 acetate and 1 part of anhydrous sodium acetate are distilled at 15 mm. pressure (oil bath: -l50 C.). The distillate is washed with water, thereupon dried with calcium chloride and ,again distilled. It is obtained in a yield of 44 parts. (i. e. a theoretical yield of 67%) and shows the boiling point 43 C. at 15 mm. pressure. We claim: a

1. The processwhich comprises causing interaction between an aliphatic Qacylated fl-hydroxynitrocompound having at most eight carbon atoms in the alcohol residue of the ester 7 and an alkaline reacting substance, the latter acetate and 5 parts of anhydrous sodium acetate are distilled under reduced pressure (15 mm). ,Wi-thin 12 hours a mixture consisting of acetic acid and unsaturated nitro compound distils over at about 60 C. The distillate is washed with water, thereupon dried with calcium chloride and being employed. in an amount below the stoichiometric one.

2. The process as claimed in claim 1 wherein the alkalinereacting substance is employed in an amount betweenabout 0.1 and about 10% calculated upon the amount of aliphatic O.acylated 'p-hydroxynitrocompound.

' v HERBERT SCHWARZ.

JOHANNES NELLES. 

